DE2243621A1 - CHROMOPHORUS SUBSTITUTED VINYL HALOMETHYL S-TRIAZINE - Google Patents

Description

M 3174

PATENT LAWYERS
Dr.-tng.H * :: SRU3CHKE LR

Au-usl-vi, o.i.-.- OwaQs 6S

Minnesota Mining and Manufacturing Company, Saint Paul, Minnesota 55101, V.St.v.A.

Chroniophore-substituted vinyl-halomethyl-js-triazine '

The invention relates to chromophore-substituted vinyl-halomethyl-s_-triazine-Verb indications and radiation-sensitive Masses and elements in which these compounds are used.

Iodoform and carbon tetrabromide are two compounds that produce halogen-containing free radicals when exposed to light are capable, which are known from the art. These free radical generating compounds have quite a bit limited spectral sensitivity, namely at wavelengths in the ultraviolet region, which are smaller than can normally be used from conventional sources. So they don't have that Ability to effectively thin out the emitted radiant energy of the high ultraviolet and visible regions? their ability or the yield to generate free radicals is reduced.

As a result of this ineffective use of radiation because of the narrow spectral sensitivity, compounds with the Free radical generating compounds combined, which serve to expand their spectral responsiveness it. In reality, the additional connection shows a wide one

309810/1185

spectral responsiveness, and it is assumed that after absorption of the radiation in a partly unexplained manner, the absorbed Energy is transmitted to the free radical generating compound, which is then able to perform its function exercise, i.e. generate free radicals. These image forming compositions are opposed to visible light because of their presence sensitive to two components, the halogenated free radical source and the dye; you are not fully satisfactory, since they were selected with regard to compatibility with one another and with the constituents of the mass Need to become. In addition, it is often difficult to achieve intimate mixing and the right weight balance between the to achieve both components.

The aim of the invention are compounds that generate free radicals on irradiation, with a broad spectral response, preferably in the visible light range. Another target are compounds that contain a light-unstable halogen Grouping and a chromophoric group contained within a molecule, the need for a combination of connections to be eliminated. The aim is also compounds that are extremely effective absorbers for radiation from conventional Light sources, in particular sources of visible light, represent and photopolymerizable and photocrosslinkable Masses and elements usable in printing, duplicating, copying and other image-forming systems, which contain such compounds. Still other objects will appear from the following description of the invention.

The objects of the invention are achieved with ^ -triazine compounds, by at least one halomethyl group, preferably are substituted by a trihaloraethyl group and by a chromophores, with the triazine ring through ethylenically unsaturated Groups conjugated moiety, this compound generating free radicals when excited by actinic radiation capable of a wavelength of about 330 to about 700 "/ u is.

3 0 9 8 10/1 185 originally inspected

Preferred chromophore substituted vinyl halomethyl-js-tri Azin compounds can be represented by the formula

CCU-C C- (CH = CH) -W Formula I.

⁵ I! - I ⁿ NN

in which Q is bromine or chlorine, P is -CQ ₅ , -NH ₂ , -NHR, -NR ₂ or -OR, with R being phenyl or lower alkyl (lower alkyl here means an alkyl group with no more than 6 Carbon atoms); η is an integer from 1 to 3 »and W is an optionally substituted aromatic or heterocyclic nucleus or

Formula II

represents wherein Z is oxygen or sulfur and R is hydrogen, a lower alkyl or phenyl group. Naturally when ¥ is an aromatic or heterocyclic nucleus, the ring may optionally be substituted. Without an exhaustive one here To try to list substituents, the following are typical: chlorine, bromine, phenyl, lower alkyl (an alkyl group with no more than 6 carbon atoms ), Nitro, phenoxy, alkoxy, acetoxy, acetyl, amino and alkylamino.

The s ^ -triazine compounds described above produce free ones Radicals when they are irradiated with actinic radiation of a wavelength of about 330 to about 700 m / u. the end For this reason, the compounds can be used as photoinitiators in light-sensitive compositions and elements. So can be incorporated into polymerizable, crosslinkable and expression compositions for use in the manufacture of Relief printing plates, photo etching grounds and photographic

309810/1185

ORIGINAL INSPECTED

Elements.

The compounds of the invention are the condensation reaction products certain methyl-halomethyl-ε-triazines and certain aldehydes or aldehyde derivatives.

Those used to prepare the compounds of the invention Methyl-halomethyl-s_-triazines have the structure:

CCU-C ^ C-CH,

Ί ' Formula I II

NN

wherein Q and P have the same meaning as in formula I.

Suitable methyl-halomethyl-s-triazines are, among others: 2,4-bis- (trichloromethyl) -6-methyl-ε-triazine 2,4-bis- (tribromomethyl) -6-methyl-ε 3-triazine 2,4 bis (dichloraethyl) -6-methyl-£ ä-triazine 2-trichloromethyl-4-me ^- thoxy-6-methyl £ -triazine _{2-trichloromethyl-4-phenoxy-6-methyl-i-s-triazine} 2- Trichloroethyl-4-diethylamino-6-methyl-s_-triazine 2-tribromomethyl-4-methylamino-6-methyl-ε-triaisine 2-tribromomethyl 1-4-amino-6-methyl-iB-trlaz in.

The preferred methyl-halomethyl-ε-triazine for use in the preparation of the compounds according to the invention is 2,4-bis (trichloromethyl) -6-methyl-s.-triazine, which Chromophore-containing vinyl-bis- (trichloromethyl) -s-triazines results in the most preferred chromophore-containing vinyl halomethyl-s, -triazines represent the invention.

In general, the methyl-halomethyl- ε -triazines by the Cotrimerization of organic nitriles and haloacetonitriles according to the teachings of Wakabayashi et al., Bulletin of the Chemical Society of Japan, 42, 2924-30 (1969).

309810/1185 original inspected

Suitable aromatic and heterocyclic aldehydes, which with the methyl-halomethyl-s ^ triazines for the synthesis of the invention Compounds react, have the formula

Formula_ IV

O = c | - (CH = CH) - (-, ρζ / Ι ^ "- 1

where η and ¥ have the same meaning as in formula I. Suitable aldehydes include: aromatic aldehydes, e.g. Benzaldehyde, 4-chloro-benzaldehyde, 3-nitro-benzaldehyde, Benzaldehyde-4-sulfonic acid, benzaldehyde-4-dimethylsulfonamide, Benzaldehyde-2-carboxylic acid, benzaldehyde-2-carboxylic acid methyl ester, Cinnamaldehyde, anisaldehyde, 3> 4-diphenoxy-benzaldehyde, 4 [2'-nitro-phenyl] -benzaldehyde, 4-phenylazobenzaldehyde; aromatic polyaldehydes such as terephthalaldehyde; heterocyclic aldehydes, e.g. 3-pyrrole aldehyde, 2-phenyl-4-oxazolecarboxaldehyde, 3-benzopyrrole aldehyde, benzoazole-2-carboxaldehyde, Benzthiazole-2-carboxaldehyde, benzoxazolylidene acetaldehyde; and heterocyclic polymethine aldehydes used for the synthesis of Cyanine dyes are used as, according to Hamer, "Cyanine Dyes and Related Compounds ", Interscience Publishers, 1964.

Many of the aldehydes of Formula IV suitable for use in preparing the compounds of the invention are available commercially. Other suitable aldehydes can be prepared according to the method taught by Pyman, J. Chem. Soc., 101 , 542 (1912) for the preparation of imidazole-2-carboxaldehydes and the method for the preparation of heterocyclic aldehydes from the corresponding oximes according to Forman in US Patent 3 150 125 are produced »

Suitable aldehyde derivatives with the methyl-halomethyl-s, - -triazines for the synthesis of the compounds according to the invention react, have the formula

309810/1185

ORKaINAL fNSPEGTED

Formula V

wherein R, Z and η have the same meaning as in formula II; D is a group that will react with reactive methylene groups including such groups as arylamino, e.g., -NH (CgH ₁ -); Acetarylamino, e.g., -N (CgH ^) - COCH ,; Alkoxy, for example -OC ^ IL ·; and alkylthio, for example -SCH,; and X is an anion such as chloride, bromide, iodide, sulfate, toluenesulfonate, ethoxyethyl sulfate. These aldehyde derivatives are quaternary salts with -NH (C ₆ H ₅ ), -N (C ₆ H ₅ ) COCH ,, -OC ₂ H ₅ and -SCpHpj groups, which are linked to one or more vinylene segments heterocyclic compound are bonded with a quaternized nitrogen. Such compounds find extensive use in the photographic industry as intermediates for the preparation of sensitizing dyes. Examples of such intermediates which can be used to prepare the vinyl halomethyl-s ^ -triazine compounds of the invention are 2- (2'-acetanilidovinyl) -benzoxazole-ethiodide (i.Orig.ethiodide), 2- (2 ' -Acetanilidovinyl) - -benzthiazole-ethyodide, 2- (4'-acetanilidobutadienyl) -benzoxazole-ethyodide, and intermediates such as

H ₃ C-S-C-S ^ ; C = CH-CH = C ^ Cl W ; NC C
I.
C ₂ H ^ N ^
C ₂ H ₅

Suitable aldehyde derivatives of formula V are compounds commonly used in the photographic industry for synthesis optical phosensitizers can be used. These connections are well described in technology, a compilation

309810/1185 _{0R1Q1NAL1NSPECTE0}

version of the same can be found in Hämer "Cyanine Dyes and Related Compounds ", pp. 116-147," Interscience Publishers, 1964.

One method by which photoinitiator compounds of the invention are prepared is the condensation of the methyl halomethyl-3-triazines with the aldehydes under conditions typical of the well-known Knoevenagel reaction for the condensation of aldehydes with reactive methylene compounds are. The preparation of 2,4-bis (trichloromethyl) -6-styryl-i3-triazine in toluene containing piperidinium acetate as a catalyst under reflux is an example of this preparation process. The reaction can be carried out in the presence of other solvents including pyridine, benzene, ethyl acetate, methanol, ethanol, tert-butanol, xylene, acetic acid, acetic anhydride, tetrahydrofuran, and mixed solvents. Since water is formed during the reaction, it is also advantageous to provide for its removal, for example, by codistillation with solvent or reaction with the solvent. The time and temperature of heating required for the condensation reaction will depend on the particular compounds being condensed and the catalyst chosen for the reaction. In general, temperatures of about 25 to 150 ^° C. within 1 to about 24 hours are sufficient to allow the reaction to proceed. The reaction is preferably carried out at temperatures of about 50 to 130 ^° C. for about 3 to 12 hours. The condensation reaction can also be carried out in the absence of solvents simply by heating the two reactants together with a catalyst at temperatures from 100 to about 140.degree.

Because of the reactive nature of the halomethyl group towards nucleophiles, the preferred catalysts for the Condensation reaction of the methyl-halomethyl-js-triazine with Aldehydes and aldehyde derivatives salts, such as, for example, piperidinium acetate.

309810/1186

In another method of synthesizing the photoinitiators of the invention, methyl-halomethyl- £> -triazines are used with various ß-anilino, ß-acetoxy-anilino and ß-alkylthio - Intermediate compounds condensed that can be used in the manufacture of cyanine dyes. Conditions for implementation these condensations are the same as those used for the condensation of methyl-halomethyl-j [-triazines with aldehydes, as described above.

The photoinitiators of the invention with the structure shown in Table 1 are particularly valuable.

Table 1

Photoinitiator Melting
⁰ C Absorption
maximum Absorbance
coefficient AA ^
C1, CC C-CH = CHC \>
³ H ι W
NN
V
I. 156-158 335 2.97 CCl ₅

2. Cl-CC ^X C- (CH = CH) ₉ ^ Λ 147-149 378 3.68 ⁵ II! ^l  V /

N N

3. C1, C-C C-CH = CH-C V) -Cl 199-201 343 3.03 2 j) V /

CCl ₅

309810/1185

ORlGlNAtINSPECTEO

ti , NN

CCl

-9- Table 1 (continued)

190-192

^ -OCH,
- / 3

Cl-CC
3

: -C ^ C-CH = CH-Vy-OCH-

I) I ^ = ^

N N ■ OCH,

186-187

2243821

377

394

6. Cl-CC ^N C-CH = CH- ^ VOCH,

CCl.

OCH.

157-158

401

7. Cl-CC ^N

Ii Y N N

> 23Od,

468

CCl.

I) ί

N N

CCl,

CH.

CH.

Cl ^ CC ^N C- (CH = CH) "-

f / i ^

ecu

220 ^e

i80-182

491

495 0.71

309 810/1 1 8 B.

2 2 A 3 ο 2 1

-10- Table 1 (continued)

10. Cl ₃ CC \ -CH = CH - ^) - OC ₅ H ₁₁ 128-129 380 3.54 NN

I.
CCl ₃

11. C1-.C

³ Il I

-C ^ C-CH = CH-CH = C If J 155-157 488 4.00

NN V

VC ₂ H ₅

I.
CCl-

12. Cl-.Ce '^ C-CH = CH-C ^175d * ⁴ ^ ^{7 2} ' ¹²

13. H ₀ NC ^ C-CH = CH- ^ ~ VoCH, 248-249 340 3.32

2, ι, Vss / 3

N _{v χ} Ν

^s c '^

f
CCl ₃

a. determined on the Kofler heating block

The photoinitiators of the invention can be used in particular in light-sensitive compositions which are used in various image-forming systems where increased light edges are desired. For example, the photopolymerizable Hansen containing the photopolymerizable agents according to the invention are of importance for the production of clusters which are used in the field of hirokupiereni, and

3 0 9 8 1 0/1 1 0 H bad original

2243521

especially for the production of useful elements for reflex copying. They are also important for elements which can be used in the production of lithographic photopolymer plates. The photoinitiators can also be used in light-sensitive non-silver masses should be present, which in Photo-reproduction systems based on acid release are useful, as in those disclosed in US patents 3,512,975 and 3,525,616 proposed systems, and in systems in which color printouts or bleaching images are formed will.

The photopolymerizable compositions in which the photoinitiators according to the invention can advantageously be used are usually composed of an ethylenically unsaturated, chain-growing addition polymerizable compound initiated by free radicals! a photoinitiator and optionally one or more fillers, binders, dyes, polymerization inhibitors, color precursors, oxygen scavengers, etc. together. The s-triazine compounds of this invention are present in an amount sufficient to cause said polymerizable compound to polymerize. Suitable component ratios are as follows: per 100 parts of polymerizable compound can be 0.0005 to 10 parts of photoinitiator, from 0 to 200 parts of filler, from 0 to 200 parts binder and 0 to 10 or more parts of dyes, polymerization inhibitors, color precursors _t oxygen Anger, etc., as are required for a specific use of the photopolymerizable composition, be present. Preferably, 1 to 7> 5 parts of photoinitiator and 25 to 150 parts of binder are used per 100 parts of polymerizable compounds.

Suitable ethylenically unsaturated, free radical initiated, chain-growing addition-polymerizable compounds are alkylene or polyalkylene glycol diacrylates, e.g. ethylene glycol diacrylate, Diethylene glycol diacrylate, glycerine diacrylate, Glycerin - triacrylate, ethylene glycol diraethacrylate, 1,3-propane

t.r i.o'l-t-rimiiUiHorylat, 1, A-Cycl oheyandiol-diacrylat, Pentaery-

309810 / 118b

ORIGINAL. JNSPECTEO

thritol tetramethacrylate, pentaerythritol triacrylate, sorbitol hexacrylate; Bis [1- (3-acryloxy-2-hydroxy)] - p-propoxyphenyl-dimethylmethane, Bis [1-f (2-acryloxy)] - p-ethoxyphenyl-dimethylmethane, Trishydroxyethyl isocyanurate trimethacrylate, the bisacrylates and bis-methacrylates of polyethylene glycols a molecular weight of 200-500 and the like; unsaturated amides, e.g., methylene bisacrylamide. Methylene-b-methacrylamide, 1,6-hexamethylene-bisacrylamide, diethylene-triamine-trisacrylamide, ß-methacrylaminoethyl methacrylate; Vinyl ester, like Divinyl succinate, divinyl adipate, divinyl phthalate, whereby the preferred ethylenically unsaturated compounds pentaerythritol tetraacrylate, Bis [p- (3-acryloxy-2-hydroxypropoxy) phenyl] - dimethyl methane and bis [p- (2-acryloxyethoxy) phenyl] dimethyl methane are. Mixtures of these esters can also be used, as can mixtures of these esters with alkyl esters of the Acrylic acid and methacrylic acid, including the esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate; Styrene, diallyl phthalate and the like.

In the preparation of the photosensitive compositions, the components are mixed together and in any order stirred or ground to form a solution or uniform dispersion. The photosensitive elements are by mounting a suitable photosensitive composition on a suitable base or support with a dry thickness of about 0.000127 cm to 0.1905 cm and drying the Cover made.

Suitable bases or supports for the photosensitive compositions include metals, e.g. steel and aluminum plates, Sheet materials and films, and composed of various film-forming synthetic or high polymers Films or plates, including addition polymers, e.g. vinylidene chloride, vinyl chloride, vinyl acetate, styrene, Isobutylene polymers and copolymers; linear condensation polymers, e.g. polyethylene terephthalate, polyhexamethylene adipate, Polyhexamethylene adipamide / adip, Iat.

3098-0 / 1 185

For example, an element for reflex copying is provided by Coating of a polyester film with a photosensitive mass prepared under darkroom conditions, which by thorough mixing of 100 parts of trimethylol propane trimethacrylate, 166 parts of polyvinyl butyral and 6.6 parts of a photoinitiator according to the invention, such as 2,4-bis (trichloromethyl) - -o-p-methoxy-styryl-s.-triazine in 3,300 parts of a solvent, such as ethylene dichloride. The coating is dried on the sticky surface with another Polyester film coated and cut into elements of suitable dimensions. The received items are ready to be copied Used by originals that can be black and white or differently colored by placing the item on the original and exposes it to radiation through the element. After exposure, the coated polyester film is removed and The exposed element is developed to be a negative of the original by dusting it with a toner powder that adheres to the sticky unexposed areas, but not in the photopolymerized areas exposed areas adheres to reveal.

The invention is illustrated more specifically by the following examples.

example 1

Production of the photosensitizer 2,4-bis (trichloromethyl) - -6-p-methoxystyryl-s-triazine.

45 parts of piperidinium acetate are added as a condensation catalyst to a mixture of 330 parts of 2,4-bis (trichloromethyl) -6-methyl-s ^ triazine and 149 »6 parts of p-anisaldehyde in 1 liter of toluene. The mixture is heated to reflux and the released water is collected in a Dean-Stark extractor. After collecting the theoretical amount of water, most of the toluene is removed by distillation and the resulting mixture is cooled. The precipitated solid is filtered off and washed several times with petroleum ether and three times with cold ethanol. A 77% yield is recorded. An analysis sample, melting point 190-192 ⁰ C, is

3 0 9 810/1185

obtained by recrystallizing the product from a mixture of ethanol-ethyl acetate.

The reaction can be carried out in the absence of solvent by thermal melting of the triazine and the aldehyde in the presence of piperidinium acetate. The molten mixture is heated to 14O ⁰ C (oil bath temperature) 60 minutes. Recrystallization yields pure product, mp, 190-192 ⁰ C (compound 4 of Table 1).

Example 2

Preparation of 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1 , 3-butadienyl) -iä-triazine.

A mixture containing 16.6 parts of 2,4-bis (trichloromethyl) -6-methyl-s-triazine, 9 »6 parts of p-dimethylaminocinnamaldehyde and 3.6 parts of piperidinium acetate in 65 parts of toluene was heated to reflux (approx 1 hour) until the theoretical amount of water was caught in a Dean-Stark trap. Upon cooling, shiny black needles separated out, which was then collected by filtration wurden.Diese crystals were slurried in hot ethanol, and 14 parts of product (Compound 7 of Table 1) blue-black in the form of shiny needles melting at 218-2Ä) ⁰ C (Kofier heating block) insulated.

Example 3

Preparation of a merocyanine dye, 2,4-bis (trichloromethyl ) -6- (N-ethy 1-2 (3H) -benzoxazolylidene) -ethylidene-s-triazine.

A mixture of 9.78 parts of 2- (N'-acetoxyanilinovinylidene) -N-ethylbenzox-azolium-p-toluenesulfonate, 9.90 parts of 2,4-bis (trichloromethyl) -6-methyl-£ j-triazine and 50 parts Pyridine was refluxed for 0.5 hour. 16 parts of methanol were added and it was continued for an additional 15 minutes Heated to reflux. The reaction mass was then dissolved in 200 parts of water containing 20 parts of 30% ammonium hydroxide,

309810/1185

poured and extracted with benzene. The extracts were washed with dilute HCl, to give over anhydrous MgSO- dried and concentrated to a red glassy _material,% which solidified upon addition of hexane. 5 »6 parts of crude products (compound 11 in Table 1) were collected, melting point 125-130 ° C. Column chromatography using neutral alumina and benzene as the solvent gave approximately 2.0 parts of the desired product, m.p. 155-157 ° C, which contained a minor impurity as indicated by NMR analysis.

Example 4

The preparation of 2-trichloromethyl-4-amino-6-p-methoxystyryl-s_-triazine.

To a 5 parts of 2,4-bis (trichloromethyl) -6-p-methoxystyryl-iS-triazine 9 parts of 30% ammonium hydroxide were added to a solution containing 57 parts of dioxane. After 5 minutes a precipitate began to form at room temperature. After 1 hour this solid was collected by filtration, Washed with 2: 1 dioxane / methanol and dried to give 3.8 parts of product (compound 13 of Table 1) as easily yellow solid, m.p. 248-249 ° C

Example 5

Explanation of the preparation of photosensitive elements using the chromophore-containing elements according to the invention Vinyl-j ^ -triazines and the spectral responsiveness of some of the connections in such elements.

A 5 »0 part Butvar B-72A (trade name for a polyvinyl butyral resin from Monsanto Chemical Co.), 3.0 parts of trimethylol propane trimethacrylate and 0.2 parts of 2,4-bis (trichloromethyl ) -6-p-methoxystyryl-s-triazine in 100 parts of ethylene dichloride containing solution was made 0.05 mm with a knife wet on polyester film. After that the solvent was evaporated, the tacky coating was overlaid with another polyester film and the sandwich was then

309810 / 118S

10 seconds with a tungsten iodide lamp through a photographic Step wedge exposed. The films were peeled off and the coating was peeled off using a 3M Brand System A-90 (Trade name) fusible toner powder dusted on the tacky unexposed areas but not on the photopolymerized regions adhered. A permanent, non-smearing positive was obtained according to the 4 open levels made on the wedge.

Similar constructions were made using the same Quantities (0.2 parts) of the photoinitiators listed in Table 2 and their spectrum of activity individually measured using a wedge spectrograph designed for laboratory use. The cited observed Responsibilities were correct within the experimental error with the absorption spectrum and maximum of these materials.

Table 2

Approximate

Photoinitiator absorption spectral maximum response

Connection 4 of Table 1 377 m / u 380-440 m / u Compound 5 of Table 1 394 m / u 390-450 nyu Compound 8 of Table 1 491 m / U 480-560 nyu

Example 6

Manufacture of printing plates to illustrate the superior Effectiveness of the chromophore-containing photoinitiators according to the invention in the presence of oxygen compared to conventional ones free radical initiators.

A number of cast coatings were placed on anodized aluminum panels (commercially available as Western Granite Grain (trade name) from Western Litho and Supply Company) using homogeneous solutions in ethylene dichloride manufactured:

309810 / 118S

Formvar 15 / 95S (trade name for a polyvinyl formal resin, available from Monsanto

Chemical Co.) 7.38

VMCH vinyl resin (trade name for a vinyl acetate / vinyl chloride / maleic anhydride copolymer, available from Union Carbide Co.) 2.46

Trimethylol propane trimethacrylate 6.00

Trismethacrylate of trishydroxyethyl isocyanurate 2.00

Cyan XR-55375B (trade name for a phthalocyanine pigment available from American CyanamidJ) 1.22

Initiator (see Table 3) 0.40

The weights of the coatings were about 0.216 mg / cm after drying at 60.00 ⁰ C for 2 minutes.

The panels were exposed every 70 seconds through a step wedge in a vacuum frame using a 135 Amp. High Intensity Photo 118 Carbon Are Rod (trade name, Union Carbide) reflective source at a distance of 137 »2 cm. For development, they were coated with a solution containing 35% n-propyl alcohol, 60 % distilled water, 1.5 % ammonium sulfate and 1.5% ammonium dihydrogen phosphate. The unexposed areas were removed using a 3M Brand (trade name) Developing Pad with an even, light to moderate amount of abrasion. Table 3 shows the relative efficiencies of the various photoinitiators that were used, based on the number of levels that were developed. It can be seen that 11 steps were developed on plates made using the chromophore-containing photoinitiators of the invention, while no more than 7 steps were developed on plates using photoinitiators suggested by the prior art.

309810/1185

Table 3 Photoinitiator

1. 0.4 parts of benzoin methyl ether 0-1

2. 0.4 parts of anthraquinone 0-1

3. 0.4 parts phenanthraquinone 0-1

4. 0.4 part of 2-ethyl-9,10-dimethoxyanthracene 0-1 0.4 parts of iodoform

5. 0.4 parts iodoform 0-1

6. 0.4 part of ethyl-9,10-dimethoxyanthracene 7 0.4 parts of 2,4,6-tris (tribromomethyl) -s_-

-triazine, "~

7. 0.4 part of 2-ethyl-9,10-dimethoxyanthracene 3 0.4 parts 2.4 bis (trichloromethyl) -6-

methyl-s_-triazine

8. 0.4 part of 1- (p-methoxyphenyl) -3- (p-diphe- 4

nylaminophenyl) -2-propen-l-one 0.4 parts 2,4-bis (trichloromethyl) -6- -methyl-si-triazine

9. 0.4 parts of chromophore-containing photo ₁₁

initiator (compound 4 of table 1)

10. 0.4 parts of chromophore-containing photo initiator (compound 5 of table 1)

Example 7

Explanation of the usefulness of the chromophore-containing Photoinitiators in photo-reproduction systems based on the release of acid.

A photosensitive mass that

Butvar B-72A (trade name) 2.5 parts

p-Dimethylaminophenyl-bis- (2-methyl-

indolyl) methane 1.0 part

Compound 4 of Table 1 0.5 parts

Methanol / ethylene dichloride 3.0 parts

contained, was drawn down to 0.075 mm wet on polyester film,

309810/1 165

After exposure, a deep fuchsine color was formed, which is characteristic of the oxidized form of the leuco dye is.

In a similar way, the leukobase gave 2-p-dimethyl- -styrylquinoline and the leuco dye leuco crystal violet Expression images based on photolytic acidification and based on photooxidation processes when used instead of p-dimethyl-aminophenyl-bis- (2-methylindolyl) -methane became.

Claims

3UyB10 / 1185

Claims (10)

-20- M 3174 Patent claims s_-triazine with at least one trihalomethyl group and at least one chromophoric group conjugated to the triazine ring by ethylenically unsaturated groups, said compound when excited by actinic radiation having a wavelength of about 330 to 700 millimicrons is capable of generating free radicals. 2. A compound according to claim 1, characterized in that said trihalomethyl group from the class: -CCl- and -CBr, is selected. 3. Compound according to claim 1, characterized in that said chromophoric grouping is one with the ij-triazine ring has conjugated aromatic or heterocyclic nucleus. 4. Composition containing an ethylenically unsaturated, chain-growing addition polymerizable, initiated by free radicals Compound and at least one free radical generating compound, characterized in that the free radical supplying compound a s_-triazine with at least one trihalomethyl group and at least one to the triazine ring chromophoric grouping conjugated by ethylenically unsaturated groups, this compound when excited capable of generating free radicals by actinic radiation of a wavelength of about 330 to 700 millimicrons is. 5. Composition according to claim 4, characterized in that said trihalomethyl group from the class: -CCl, and -CBr, is selected. 6. Composition according to claim 4, characterized in that said chromophoric grouping one with the s, -triazine ring has conjugated aromatic or heterocyclic nucleus. 309810 / 118S 7. Compound of Formula N
CGL ₅ -C ^ C- (CH = CH) -W ■ ³ Ii l ⁿ . N N wherein Q is bromine or chlorine, P is -CGU, -NH ₂ , -NHR, or -OR with R being phenyl or lower alkyl- (lower alkyl here means an alkyl group with not more than 6 carbon atoms); η is an integer from 1 to 3; and ¥ an optionally substituted aromatic or heterocyclic nucleus or 1 represents, in which Z is oxygen or sulfur and R is water, substance, a lower alkyl or phenyl group, this compound when excited by actinic Radiation with a wavelength of about 330 to 700 millimicrons is capable of generating free radicals. . 8. A compound according to claim 7, characterized in that Q is Cl and P is -CCl. 9. Composition containing an ethylenically unsaturated, free radical initiated, chain-growing addition polymerizable Compound and at least.eine free radical generating compound, characterized in that these free radicals supplying compound is a compound of the formula 309810/11 SB CQ_-C ^ C- (CH = CH) _n W is where Q is bromine or chlorine, P is -CQ 1, -NH ₂ , -NHR, -NRp or OR where R is phenyl or lower alkyl (lower alkyl here means an alkyl group with not more than 6 carbon atoms); η is an integer from 1 to 3 »and W is an optionally substituted aromatic or heterocyclic nucleus or -CH = C N ' R ¹ represents where Z is oxygen or sulfur and R is hydrogen, a lower alkyl or phenyl group, said compound producing when excited by actinic radiation having a wavelength of about 330 to 700 millimicrons Is capable of generating free radicals. 10. Composition according to claim 9, characterized in that Q is equal to Cl and P is equal to --CCl-. 309 810/1185